Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
  • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
  • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
  • C07D213/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
  • C07D213/57—Nitriles

Definitions

• the present invention relates to novel pyridyl­acetonitrile derivatives, and nonmedical fungicides or germicides, especially agricultural fungicides, containing the pyridylacetonitrile derivatives as an effective ingredient.
• An object of the present invention is to provide novel pyridylacetonitrile derivatives, and nonmedical fungicides or germicides, especially agricultural fungicides, containing the pyridylacetonitrile derivatives as an effective ingredient.
• a pyridylacetonitrile derivative inclusive of acid salts and metal complexes thereof, of the general formula (I) wherein X is a halogen atom or a phenylethynyl group, Y is a hydrogen atom, a halogen atom, a methyl group or a trifluoromethyl group, R is a lower alkyl group or a phenyl group which may be substituted or unsubstituted with a halogen atom.
• nonmedical fungicides or germicides comprising, as an effective ingredient, the pyridylaceto­nitrile derivatives represented by the general formula (I), or the physiologically acceptable salts or metal complexes thereof.
• novel pyridylacetonitrile derivatives represented by the above mentioned general formula (I).
• X represents a halogen atom or a phenylethynyl group, preferably chlorine, fluorine or phenylethynyl
• Y represents a hydrogen atom, a halogen atom, a methyl group or a trifluoromethyl group, preferably a chlorine or fluorine atom
• R represents a lower alkyl group (preferably 1 to 6 carbon atoms) or a phenyl group which may be substituted or unsubstituted with a halogen atom (preferably chlorine or fluorine), more preferably alkyl group having 1 to 4 carbon atoms, most preferably a methyl group, an ethyl group or a n-­propyl group.
• the acid salts of the pyridylacetonitrile derivatives (I) are those which are formed from the compounds of the general formula (I) and inorganic or organic acids.
• the typical examples of the inorganic or organic acids are hydrochloric acid, hydrobromic acid, sulfuric acid, oxalic acid, sulfonic acid, and the like.
• the metal complexes of the pyridylacetonitrile derivatives (I) are those which are composed of the compounds of the general formula (I) and metal salts.
• the preferred metal complexes can be represented by the following general formula (II) wherein X, Y and R are as defined above and M is a metal atom and X′ is a counter ion, and n and m each represents integers of 1 to 4.
• M are aluminum, manganese, cobalt, iron, nickel, cupper or zinc, preferably cupper or zinc.
• the preferred examples of X′ are chloride, bromide, iodide, sulfate, phosphate, nitrate, carbonate or acetate ion.
• novel pyridylacetonitrile derivatives of the general formula (I) according to the present invention can be produced by the process shown by the following reaction formula:
• X, Y, and R are the same as that defined above, and L represents, lithium, MgCl, MgBr or MgI.
• the reaction is preferably carried out in the presence of an organic solvent at a temperature of from -80°C to the boiling point of the solvent, more preferably from -5°C to 20°C.
• the reaction time preferably ranges from 1 to 24 hours.
• the preferred molar ratio of the compound (III) and the compound (IV) is 1:1 to 1:1.5.
• organic solvent examples include aliphatic hydrocarbons such as hexane, heptane or petroleum ether, aromatic hydrocarbons such as benzene, toluene or xylene, and ethers such as diethylether, diisopropylether, dioxane, tetrahydrofuran or diethylene­glycol dimethylether.
• aliphatic hydrocarbons such as hexane, heptane or petroleum ether
• aromatic hydrocarbons such as benzene, toluene or xylene
• ethers such as diethylether, diisopropylether, dioxane, tetrahydrofuran or diethylene­glycol dimethylether.
• the olefins of the general formula (III) can be prepared from 3-pyridylacetonitrile by the methods as described, for example, in U.S. Patent 3,196,158 and Yakugaku Zasshi , vol. 89, pp. 188-193 (1969).
• the desired product represented by the formula (I) can be isolated and purified in any conventional manner.
• the isomer of the product (I) can be separated by silica gel chromatography.
• the compounds of the general formula (I) waherein X is a phenylethynyl group, can be also prepared by reacting the corresponding bromoderivatives (X in the general formula I is a bromine atom) with phenylacetylene in the presence of a catalyst such as palladium complex as described, for example, in Synthetic Example 3.
• the metal complexes of the pyridylacetonitrile derivatives (I), which is represented by the general formula (II), can be prepared by reacting the compound of the general formula (I) with a metal salt in the presence of an organic solvent such as methanol, ethanol, propanol, chloroform, acetone, acetonitrile or diethylether, preferively methanol or ethanol.
• an organic solvent such as methanol, ethanol, propanol, chloroform, acetone, acetonitrile or diethylether, preferively methanol or ethanol.
• the compounds according to the present invention have two asymmetric carbon atoms and, therefore, four stereoisomers are present. These isomers and their mixture are within the scope of the present invention.
• the pyridylacetonitrile derivatives or its acid salts and metal complexes in accordance with the present invention exhibit excellent fungicidal activity against various crop diseases, especially gray mold.
• the typical examples of such diseases are as follows: Rice: Blast, Helminthosporium leaf spot, Sheath blight, "Bakanae” disease, Seedling blight Wheat: Leaf rust, Stripe rust, Loose smut, Speckled leaf blotch, Spot blotch, Browing root rot, Powdery mildew Potato: Late blight, Early blight, Black scurf Soybean: Downy mildew, Cercospora leaf spot, Mycosphaerella sojae, Sclerotinia rot, Rust, Purple stain Adzuki bean: Leaf spot, Rust, Leaf spot, Powdery mildew Peanut: Brown leaf spot, Leaf spot, Sclerotinia rot Tobacco: Brown spot, Black shank, Sclerotini
• the effect of the compounds according to the present invention is not only preventive, but also curative. Moreover, the effect persists for long term and the phytotoxicity, especially growth suppression, caused by the fungicides in the present invention is extremely slight.
• the compounds may be directly used.
• the present compounds can be formulated with solid carriers, liquid carriers, surfactants, and other adjuvants to form various forms of preparations such as emulsions, wettable powder, suspensions and granules.
• the present pyridylacetonitrile derivatives can be formulated as an effective ingredient into the preparations in an amount of 0.1% to 99.9% by weight, preferably 0.2% to 80% by weight.
• Typical examples of the solid carriers usable in the formulation are finely divided powder or particles of kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomeceous earth, calcite, and white carbon.
• Typical examples of the liquid carriers are aromatic hydrocarbons such as xylene and methyl naphthalene; alcohols such as isopropanol, ethylene glycol, and cellosolve; ketones such as acetone, cyclo­hexanone, and isophorone; vegetable oil such as bean oil and cotton seed oil; dimethyl sulfoxide; and acetonitrile.
• Typical examples of the surfactants usable as an emulsifier, dispersing agent and/or wetting and spreading agent are anionic surfactants such as alkylsulfate salts, alkyl(or aryl)sulfonate salts, dialkylsulfosuccinate salts, polyolyoxyethylenealkylaryl ether phosphate salts, and naphthalene sulfonic acid formaldehyde condensates; and nonionic surfactants such as polyoxyethylenealkyl ether, polyoxyethylene polyoxypropylene block copolymers, and sorbitan fatty acid esters.
• anionic surfactants such as alkylsulfate salts, alkyl(or aryl)sulfonate salts, dialkylsulfosuccinate salts, polyolyoxyethylenealkylaryl ether phosphate salts, and naphthalene sulfonic acid formaldehyde condensates
• Typical examples of the adjuvants for formulation are lignin sulfonate, alginates, polyvinyl alcohol, gum arabic, carboxymethyl cellulose, and acidic isopropyl phosphate.
• the effective component of the present fungicide can be also formulated into the preparations together with one or more agents such as various conventional insecticides, bactericides, fungicides, herbicides, plant growth regulators, miti­cides, nematocides, attractants, repellents, nutrients, fertilizers, and soil structure conditioning agents.
• these preparations are expected to exhibit various wide effects.
• the mixture can be separated into the diastereomer A with larger R f value (mp. 84.7-86°C) and the diastereomer B with smaller R f value (mp. 68.5-69°C) by silica gel chromatography using a 2:1 (by volume) mixture of n-hexane and ethyl acetate as an eluent.
• Power fungicides having the following compositions were prepared by mixing the ingredients listed below at room temperature. Ingredient Parts by weight Compound listed in Table 1 or 2 3 Clay 40 Talc 57
• Wettable powder fungicides having the following compositions were prepared by mixing the ingredients listed below at room temperature. Ingredient Parts by weight Compound listed in Table 1 or 2 25 Polyoxyethylene alkylarylether 9 White carbon 16 Talc 50
• the wettable powder fungicide is thus obtained were evaluated in the Test Examples below.
• Emulsion fungicides having the following compositions were prepared by mixing the ingredients listed below at room temperature.
• Ingredient Weight in 100 ml Compound listed in Table 1 or 2 20 g Sorpol 2680® (manufactured by Toho Kagaku Kogyo K.K.) 10 g Xylene balance
• the agricultural or horticultural fungicide according to the present invention can be preferably used in an amount of 1 to 500 g, in terms of an active ingredient, per 10 are (a) when the fungicide is sprayed to the field having growing crops thereon and 0.1 to 5 kg, in terms of an acitve ingredient, per 10 are (a), when the fungicide is applied into the soil. It should be, of course, noted that the amount of the active ingredient depends upon the kinds of crops, diseases, and damages, seasons, weather, and the preparation forms of the fungicides.
• the agricultural or horticultural fungicides according to the present invention were evaluated in the following Test Examples.
• the reference compounds A to G, which were used in each test, are shown in Table 12.
• a sample solution containing a predetermined amount of the active compound was sprayed on cucumber seedlings (variety: Sagami Hanjiro) at 2 leaf stage in a pot with the volume of 200 liter/10 a and the treated cucumber seedlings were air-dried in a room.
• the treated cucumber seedlings was allowed to stand in a green house to naturally infect with the spores of Sphaerotheca fuliginea .
• n Number of leaves in each infection degree f: Index of infection degree N: Number of leaves examined. Index of infection degree Infected area (%) 0 (No infection) 0 1 (Low infection) 1-25 3 (Medium infection) 26-50 5 (Large infection) 51-100
• the sprayed wheat seedlings were allowed to stand under a dark condition at a temperature of 23°C in an R.H. of 100% for 28 hours. After 28 hours, the wheat seedlings were transferred to a green house and, after 3 days from the inocuration, a sample fungicide solution containing a predetermined amount of the active compound was sprayed on the wheat seedlings with the volume of 200 liter/10 a. After 10 days from the inoculation, the degree of the infection was calculated as follows. Five tests were carried out in each run.
• n Number of leaves in each infection degree f: Index of infection degree N: Number of leaves examined Index of infection degree Infected area (%) 0 (No infection) 0 1 (Low infection) 1-25 3 (Medium infection) 26-50 5 (Large infection) 51-100
• a sample solution containing a predetermined amount of the active compound was sprayed on cucumber seedlings (variety: Suhyoo) at 3 leaf stage in a pot at a volume of 200 liter/10 a and the treated cucumber seedlings were air-dried for 24 hours in a room.
• a spore suspension was prepared in such a way that 100 conidia of Botrytis cinerea were present in a visual area of a 100 magnification microscope and a commercially available yeast extract (1% amount) and a commercially available glucose (10% amount) were added thereto.
• the resultant suspension was inoculated by spraying. Immediately, the sprayed cucumber were allowed to stand under a dark condition at a temperature of 22°C and an R.H. of 100%. After 3 days, the degree of the infection was measured. The protection value was calculated as follows. Eight tests were carried out in each run.
• n Number of leaves in each infection degree f: Index of infection degree N: Number of leaves examined Index of infection degree Infected area (%) 0 (No infection) 0 1 (Low infection) 1-25 3 (Medium infection) 26-50 5 (Large infection) 51-100
• a 20 ml sample solution containing a predetermined concentration of the active compound was sprayed on 10 cotyledons of a kidney bean (variety: Masterpiece), which were dried in a room. After drying, the mycelia of Sclerotinia sclerotiorum grown on a PDA culture medium was inoculated after punching with a cork borer. The incubation was carried out at a temperature of 28°C and an RH of 100% for 4 days. The infected area was measured. Ten tests were carried out in each run. Controlled value (1-S/S0) ⁇ 100 wherein S: average infected area of leaves treated by an active compound S0: average infected area of no-treated leaves The results are shown in Table 6.
• a sample solution containing a predetermined amount of the active solution was sprayed on rice seedlings (variety: Jyukkoku) at 3 leaf stage in a pot with the volume of 200 liter/10 a and the treated rice seedlings were air-dried.
• a spore suspension previously prepared in such a way that 40 conidia of rice blast fungus ( Pyricularia oryzae ) were present in a visual area of a 100 magnification microscope was inoculated by spraying.
• the sprayed rice seedlings were allowed to stand under a dark condition of a temperature of 23°C and an R.H. of 100%.
• the rice seedlings were transferred to a green house and, after 10 days from the inocuration, the degree of the infection was measured.
• the protection value was calculated as follows. Three tests were carried out in each run. wherein n: Number of leaves in each infection degree f: Index of infection degree N: Number of leaves examined Index of infection degree Number of Lesion per leaf 0 0 1 1 2 2-5 3 6-10 4 11 or more
• Table 7 Antifungal activity against rice blast Compound No. Concetr. (a.i., ppm) No. of infected leaves No. of leaves in each infection degree % of Infected leaves Infection degree Chemical injury 0 1 2 3 4 1 500 206 145 48 13 0 0 29.6 9.0 - F 500 185 128 45 12 0 0 30.8 9.3 - G 500 180 151 28 1 0 0 16.1 4.2 - Control - 204 0 0 71 81 42 100 72.7
• a sample solution containing a predetermined concentration of the active compound was sprayed on cotyledons of a kidney bean (variety: Masterpiece), which were dried in a room.
• a sample solution containing a predetermined amount of the active compound was sprayed on egg plant seedlings (variety: Senryo #2) at 4-leaf stage in a pot with the volume of 200 liter/10 a on one day, four days, seven days before inoculation, and the treated egg plant seedlings were administered in a green house.
• the inoculation and the measurement of the degree of infection were carried out in the same way as described in Test Example 3.
• a second developed leaf of egg plant (variety: Senryo #12) was placed in a petri dish and the mycelia of Botrytis cinerea grown on a PDA culture medium was inoculated after punching with a cork borer on the center of the leaf.
• the incubation was carried out at 25°C under humid condition for 24 hours.
• a sample solution in 250 ppm was sprayed on the leaf at the volume rate of 20 ml per 8 plates. After air drying, the incubation was carried out at 25°C under humid condition. The diameter of the infected area was measured every day for 5 days after the application. Eight tests were carried out in each run.
• Table 11 Curative activity against gray mold of egg plant Compound No. Concentr. (a.i., ppm) Diameter of lesion (mm) 1* 2* 3* 4* 5* 1 125 10 15 17 19 19 2 125 10 15 18 20 20 5 125 10 16 18 21 22 6 125 10 17 20 22 25 7 125 10 18 20 23 25 11 125 10 15 17 19 19 12 125 10 15 17 19 19 13 125 10 15 18 20 21 A 125 10 18 23 26 30 E 125 10 18 21 22 26 Control - 10 22 31 43 55 Note: "*" is stand for the number of days between the application and observation.
• Table 12 Referance Compounds Code Chemical name Brandname & source A 3-(2,4-dichlorophenyl)-2-(1-imidazolyl)hexanenitrile JP-A-86-167668 B Validamycin A Validacin from Takeda Chemical Industries, Ltd.
• the fungicides containing, as an effective ingredient, the comopunds according to the present invention exhibit excellent antifungal effect against broad range of crop diseases.
• the present compounds When the present compounds are applied to crop fields, presistence can be exhibited. Further, the effect of the compounds according to the present invention is not only preventive, but also curative.
• the phytotoxicity against crops, especially tomato, cucumber, egg plant, green pepper, root crops, etc., caused by the fungicides of the present inveniton is extremely slight.

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• Agricultural Chemicals And Associated Chemicals (AREA)

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• 1988
  • 1988-10-05 EP EP19880116494 patent/EP0311051A3/de not_active Withdrawn

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